CN114907814A - Foaming ceramic heat-insulation fireproof silicone sealant and preparation method thereof - Google Patents

Abstract

The invention relates to the field of high polymer sealing materials, and provides a foaming ceramic heat-insulating fireproof silicone sealant and a preparation method thereof aiming at the problem that the sealant is difficult to prevent fire and block due to high-temperature pulverization and shedding, wherein the foaming ceramic heat-insulating fireproof silicone sealant comprises the following components in parts by weight: 100 parts of basic polymer, 2-25 parts of plasticizer, 20-100 parts of filler, 50-120 parts of flame retardant, 10-75 parts of glass powder, 0.5-15 parts of foaming agent, 0-5 parts of thixotropic agent, 3-20 parts of color paste, 3-15 parts of crosslinking agent, 0.2-5 parts of silane coupling agent and 0.015-0.3 part of catalyst; the base polymer is at least one of alpha, omega-dihydroxy polydimethylsiloxane and alkoxy-terminated polydimethylsiloxane. The sealant disclosed by the invention expands when heated, can form a ceramic hole structure under the condition of continuous high-temperature burning, and plays a role in fire prevention, heat insulation and plugging.

Description

Foaming ceramic heat-insulation fireproof silicone sealant and preparation method thereof

Technical Field

The invention relates to the field of high polymer sealing materials, in particular to an expanded ceramic heat-insulating fireproof silicone sealant and a preparation method thereof.

Background

In recent years, high-rise building fires frequently give people a knock on a safety alarm clock. The fireproof sealant is adopted to carry out fireproof plugging design on building gaps, so that the fire resistance limit of the curtain wall can be improved, the time of the curtain wall for resisting fire is prolonged, smoke and fire spread when the fire happens is prevented, and loss caused by the fire is reduced as much as possible. For example, patent CN1438289 discloses a neutral silicone fire-retardant sealant and a manufacturing method thereof, which achieves the purpose of fire prevention by adding a fire retardant, but the sealant prepared by the method is gradually pulverized and peeled off under the condition of continuous high temperature, so that the effect of fire blocking is difficult to achieve. Patent CN103509517A discloses a porcelainized flame-retardant fireproof silicone sealant and a preparation method thereof, which enables the sealant to form a compact porcelainized material under the condition of continuous high temperature by adding porcelainized powder, but in the process of forming the porcelainized material, the volume of a sealing material can shrink, so that cracks are generated at the sealing part to prevent the diffusion of smoke and heat, and the effect of fireproof plugging is difficult to meet. Accordingly, an ideal solution is needed.

Disclosure of Invention

The invention provides a foaming type ceramic heat-insulation fireproof silicone sealant and a preparation method thereof, aiming at overcoming the problem that the sealant is difficult to prevent fire and block due to high-temperature pulverization and shedding.

In order to achieve the purpose, the invention adopts the following technical scheme:

the foaming ceramic heat-insulation fireproof silicone sealant comprises the following components in parts by weight: 100 parts of basic polymer, 2-25 parts of plasticizer, 20-100 parts of filler, 50-120 parts of flame retardant, 10-75 parts of glass powder, 0.5-15 parts of foaming agent, 0-5 parts of thixotropic agent, 3-20 parts of color paste, 3-15 parts of crosslinking agent, 0.2-5 parts of silane coupling agent and 0.015-0.3 part of catalyst; the base polymer comprises at least one of alpha, omega-dihydroxy polydimethylsiloxane and alkoxy-terminated polydimethylsiloxane.

More preferably, the viscosity of the base polymer at 25 ℃ is in the range of 5000-.

Preferably, the plasticizer is at least one of polydimethylsiloxane, alkane mixture and polyethylene glycol. The plasticizer can weaken intermolecular force of polymers in the sealant, increase the mobility of polymer molecular chains and reduce the crystallinity of the molecular chains, thereby improving the fluidity of the sealant; the elongation, flexibility and flexibility of the sealant are improved, and the hardness and brittleness of the sealant are reduced, so that the physical and chemical properties of the sealant are improved.

Preferably, the filler is at least one of active nano calcium carbonate, light calcium carbonate, heavy calcium carbonate, diatomite, silicon micropowder, kaolin, quartz powder, titanium dioxide and fumed silica. More preferably, the average particle size of the active nano calcium carbonate is 40-100 nm; the specific surface area of the gas-phase white carbon black is 150-200m ² /g。

Preferably, the flame retardant is at least one of modified hydrated metal oxide, metal boride, antimony trioxide, ammonium polyphosphate, melamine urea cyanate and calcium aluminate.

Preferably, the glass powder is at least one of aluminum oxide, silicon dioxide, boron trioxide, lithium oxide, sodium oxide, potassium oxide, barium oxide, calcium oxide and magnesium oxide. Under the combustion condition, the ashes and the glass powder after the sealant is combusted can form a ceramic material after absorbing heat, the formed ceramic material can be harder and harder along with the rise of the combustion temperature and the extension of time, the sealant is prevented from losing the fixing and sealing effects, and the effects of isolating flame, smoke and preventing fire are achieved.

Preferably, the foaming agent comprises at least one of p-toluenesulfonyl semicarbazide, 5-phenyltetrazole, azodicarbonic ammonium carbonate, glass microspheres, and diethyl azodicarboxylate.

Preferably, the foaming agent is a glass microsphere coated by p-toluenesulfonyl semicarbazide, and the preparation method comprises the following steps:

1) selecting the density of 0.40-0.60g/cm ³ Drying the hollow glass microspheres with the particle size of 100-;

2) adding dimethyl sulfoxide into p-toluenesulfonyl semicarbazide until the dimethyl sulfoxide is dissolved, adding the hollow glass microspheres coated with the coupling agent, wherein the mass ratio of the hollow glass microspheres coated with the coupling agent to the p-toluenesulfonyl semicarbazide is 1 (2-4), stirring for 1-2h, standing overnight, filtering, and drying at the temperature of 100 ℃ and 120 ℃ for 2-4h to obtain the glass microspheres coated with the p-toluenesulfonyl semicarbazide.

The glass microsphere is a hollow closed spherical ultra-light filling material containing vacuum rarefied gas, and has the advantages of light weight, large volume, low heat conductivity coefficient, good heat insulation, dispersibility, fluidity and stability. According to the invention, the surface of the glass microsphere coated with the tosylsemicarbazide is matched with the surface of the glass microsphere to achieve a better foaming flame-retardant effect. On one hand, the decomposition temperature of the p-toluenesulfonyl semicarbazide is 220-230 ℃, the crushing temperature of the glass microspheres is as high as about 500 ℃, the external p-toluenesulfonyl semicarbazide expands and foams at about 200 ℃ after the sealant is heated, the temperature is continuously raised to 500 ℃, the glass microspheres begin to crack to release gas, and second wave foaming can be carried out; on the other hand, the benzenesulfonylamino urea is coated on the surface of the spherical glass microsphere, so that the outward expansion of the benzenesulfonylamino urea is facilitated from the perspective of expansion mechanics, the high fluidity of the spherical glass microsphere can also improve the overall fluidity of the foaming agent, the dosage of the benzenesulfonylamino urea is required to be controlled so as to avoid damaging the spherical structure due to too thick coating, and the coating of the benzenesulfonylamino urea can reduce the breakage rate of the glass microsphere in the early-stage mixing preparation process and promote each other.

Preferably, the thixotropic agent is at least one of polyamide wax and hydrogenated castor oil; the catalyst is at least one of isopropyl titanate, tetrabutyl titanate, di (ethyl acetoacetate) diisopropoxy titanate, di (acetylacetone) -1, 3-propylene dioxy titanium, dibutyltin dilaurate, dibutyltin diacetate, stannous octoate and chelated tin.

Preferably, the cross-linking agent is at least one of methyltrimethoxysilane, vinyl trimethoxysilane, methyl tributyrinoxime silane, vinyl tributyrinoxime silane and phenyl tributyrinoxime silane; the silane coupling agent is at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, urea propyl triethoxysilane, diethylenetriaminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane and glycidoxypropyltriethoxysilane. The cross-linking agent can deepen the cross-linking depth of the sealant and improve the hardness and the tensile bonding strength of the sealant; the cross-linking agent is matched with the coupling agent for use, so that the adhesive force can be further enhanced, the curing time can be adjusted, and the construction is convenient.

The invention also provides a preparation method of the foamed ceramic heat-insulation fireproof silicone sealant, which comprises the following steps:

A. putting a base polymer, a plasticizer, a filler, a flame retardant, glass powder, a foaming agent and a thixotropic agent into a kneader, controlling the oil temperature range at 110-;

B. and putting the base material, the color paste, the cross-linking agent, the silane coupling agent and the catalyst into a stirrer, controlling the vacuum degree to be 0.09-0.095MPa and the stirring frequency to be 80-120Hz, stirring for 0.5-1.5h, and removing the vacuum by nitrogen to prepare the foamed ceramic heat-insulating fireproof silicone sealant.

Therefore, the beneficial effects of the invention are as follows: (1) the foaming ceramic heat-insulation fireproof sealant can form a ceramic material with a porous structure under the action of continuous high temperature, can keep the original sealing effect under the continuous flame ablation, prevents the flame from spreading and the toxic smoke from diffusing, can play a heat insulation role through a hole structure, and ensures the safety of personnel escape under the condition of fire; (2) the foaming ceramic heat-insulating fireproof sealant has good bonding performance to building materials, no corrosion and stable storage performance.

Drawings

FIG. 1 is a test chart of the flame retardant property of the fireproof sealant of the present invention;

FIG. 2 is a test chart of the vitrification and expansibility of the fireproof sealant of the present invention;

FIG. 3 is a test chart of acid resistance, alkali resistance and water resistance of the fireproof sealant of the present invention;

fig. 4 is a diagram showing the corrosion test of the fireproof seal according to the present invention.

Detailed Description

The technical solution of the present invention is further illustrated by the following specific examples.

In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.

General examples

The foaming ceramic heat-insulation fireproof silicone sealant comprises the following components in parts by weight:

the preparation method of the sealant comprises the following steps:

A. putting a base polymer, a plasticizer, a filler, a flame retardant, glass powder, a foaming agent and a thixotropic agent into a kneader, controlling the oil temperature range at 110-;

B. and putting the base material, the color paste, the cross-linking agent, the silane coupling agent and the catalyst into a stirrer, controlling the vacuum degree to be 0.09-0.095MPa and the stirring frequency to be 80-120Hz, stirring for 0.5-1.5h, and removing the vacuum by nitrogen to prepare the foamed ceramic heat-insulating fireproof silicone sealant.

Example 1

The foaming ceramic heat-insulation fireproof silicone sealant comprises the following components in parts by weight:

base polymer	100 parts of alpha, omega-dihydroxypolydimethylsiloxane (viscosity at 25 ℃ approximately 10000 pas)
		Plasticizer	Polydimethylsiloxane 12 parts
Filler	40 parts of active nano calcium carbonate (with the average particle size of 80nm) and 10 parts of heavy calcium carbonate
		Flame retardant	105 parts of modified hydrated metal oxide and 5 parts of ammonium polyphosphate
Glass powder	10 parts of diboron trioxide and 45 parts of aluminum oxide
		Foaming agent	0.5 part of azodicarbonic ammonium
Thixotropic agent	0 portion of
		Color paste	15 parts of black paste
Crosslinking agent	3 parts of vinyl tributyrinoxime silane and 12 parts of methyl tributyrinoxime silane
		Silane coupling agent	1.5 parts of gamma-aminopropyl triethoxysilane
Catalyst and process for preparing same	0.15 portion of dibutyltin dilaurate

The preparation method of the sealant comprises the following steps:

A. putting a base polymer, a plasticizer, a filler, a flame retardant, glass powder, a foaming agent and a thixotropic agent into a kneader, dehydrating for 2 hours under the conditions that the oil temperature range is controlled at 120 ℃, the vacuum degree is controlled at 0.09MPa and the rotating speed is 50rpm, and naturally cooling to 20 ℃ to obtain a base material;

B. and putting the base material, the color paste, the cross-linking agent, the silane coupling agent and the catalyst into a stirrer, stirring for 1h under the conditions of controlling the vacuum degree to be 0.09MPa and the stirring frequency to be 100Hz, and removing the vacuum by nitrogen to prepare the foamed ceramic heat-insulating fireproof silicone sealant.

Example 2

The foaming ceramic heat-insulation fireproof silicone sealant comprises the following components in parts by weight:

base polymer	100 parts of alpha, omega-dihydroxypolydimethylsiloxane (viscosity at 25 ℃ C. of about 5000 pas)
		Plasticizer	2 portions of polyethylene glycol
Filler material	Active nano calcium carbonate (average particle size 40)nm)25 parts and silicon micropowder 25 parts
		Flame retardant	90 parts of calcium aluminate and 10 parts of melamine
Glass powder	50 parts of diboron trioxide
		Foaming agent	Glass microsphere 0.5 part
Thixotropic agent	0 portion of
		Color paste	10 portions of black paste
Crosslinking agent	12.5 parts of methyl tributyl ketoxime silane and 2 parts of vinyl tributyroxime silane
		Silane coupling agent	1.2 portions of gamma-urea propyl triethoxy silane
Catalyst and process for preparing same	0.1 part of dibutyltin dilaurate

The preparation method of the sealant comprises the following steps:

A. putting a base polymer, a plasticizer, a filler, a flame retardant, glass powder, a foaming agent and a thixotropic agent into a kneader, dehydrating for 3 hours under the conditions that the oil temperature range is controlled at 110 ℃, the vacuum degree is controlled at 0.08MPa and the rotating speed is 40rpm, and naturally cooling to 20 ℃ to obtain a base material;

B. and putting the base material, the color paste, the cross-linking agent, the silane coupling agent and the catalyst into a stirrer, stirring for 1.5h under the conditions of controlling the vacuum degree to be 0.095MPa and the stirring frequency to be 80Hz, and removing the vacuum by nitrogen to prepare the foamed ceramic heat-insulating fireproof silicone sealant.

Example 3

The foaming ceramic heat-insulation fireproof silicone sealant comprises the following components in parts by weight:

base polymer	100 parts of alkoxy-terminated polydimethylsiloxane (viscosity at 25 ℃ C. of approximately 100000 pas)
		Plasticizer	Polydimethylsiloxane 15 parts
Filler material	25 parts of active nano calcium carbonate (with average particle size of 100nm), 15 parts of kaolin and 12 parts of quartz powder
		Flame retardant	75 parts of modified hydrated metal oxide and 30 parts of antimony trioxide
Glass powder	55 parts of aluminum oxide
		Foaming agent	0.5 part of p-toluenesulfonyl semicarbazide
Thixotropic agent	0 portion of
		Color paste	10 portions of black paste
Crosslinking agent	13 parts of methyltrimethoxysilane and 2 parts of vinyl trimethoxy silane
		Silane coupling agent	4 parts of glycidyl ether oxypropyl triethoxysilane
Catalyst and process for preparing same	0.16 part of bis (acetylacetone) -1, 3-propyldioxytitanium

The preparation method of the sealant comprises the following steps:

A. putting a base polymer, a plasticizer, a filler, a flame retardant, glass powder, a foaming agent and a thixotropic agent into a kneader, dehydrating for 2 hours under the conditions that the oil temperature range is controlled at 130 ℃, the vacuum degree is controlled at 0.095MPa and the rotating speed is 60rpm, and naturally cooling to 20 ℃ to obtain a base material;

B. and putting the base material, the color paste, the cross-linking agent, the silane coupling agent and the catalyst into a stirrer, stirring for 0.5h under the conditions of controlling the vacuum degree to be 0.095MPa and the stirring frequency to be 120Hz, and removing the vacuum by nitrogen to prepare the foamed ceramic heat-insulating fireproof silicone sealant.

Example 4

The foamed ceramic heat-insulation fireproof silicone sealant comprises the following components in parts by weight:

the preparation method of the sealant is the same as that of example 1.

Example 5

The difference from the example 2 is that the foaming agent is 0.5 part of paratoluenesulfonylsemicarbazide-coated glass microspheres, and the preparation method comprises the following steps: 1) selecting cipherDegree of 0.50g/cm ³ Drying the hollow glass microspheres with the particle size of 120 mu m, adding an aqueous solution (mass concentration is 3%) of a coupling agent phenylaminomethyl triethoxysilane, stirring for 1h, and filtering to obtain coupling agent-coated hollow glass microspheres;

2) adding dimethyl sulfoxide into p-toluenesulfonyl semicarbazide until the dimethyl sulfoxide is dissolved, adding the hollow glass microspheres coated with the coupling agent, wherein the mass ratio of the hollow glass microspheres coated with the coupling agent to the p-toluenesulfonyl semicarbazide is 1:3, stirring for 2 hours, standing overnight, filtering, and drying for 3 hours at 110 ℃ to obtain the glass microspheres coated with the p-toluenesulfonyl semicarbazide.

Example 6

The difference from example 2 is that the blowing agent is 0.25 parts p-toluenesulfonyl semicarbazide +0.25 parts glass microspheres.

Example 7

The difference from the example 2 is that the foaming agent is 0.5 part of paratoluenesulfonylsemicarbazide-coated glass microspheres, and the preparation method comprises the following steps: 1) selecting the density of 0.50g/cm ³ Drying the hollow glass microspheres with the particle size of 120 mu m, adding an aqueous solution (mass concentration is 3%) of a coupling agent phenylaminomethyl triethoxysilane, stirring for 1h, and filtering to obtain coupling agent-coated hollow glass microspheres;

2) adding dimethyl sulfoxide into p-toluenesulfonyl semicarbazide until the dimethyl sulfoxide is dissolved, adding the hollow glass microspheres coated with the coupling agent, wherein the mass ratio of the hollow glass microspheres coated with the coupling agent to the p-toluenesulfonyl semicarbazide is 1:5, stirring for 2 hours, standing overnight, filtering, and drying for 3 hours at 110 ℃ to obtain the glass microspheres coated with the p-toluenesulfonyl semicarbazide.

Performance testing

The foamed ceramic heat-insulating fireproof sealant prepared in each embodiment is tested according to GB/T23864-2009, and the test results are detailed in the following table.

As can be seen from the table above, the foamed ceramic heat-insulating fireproof sealant prepared by the invention has excellent flame retardance, vitrification and corrosion resistance. Compared with the example 2, in the example 5, the glass microspheres of the foaming agent are replaced by the glass microspheres coated with the tosylsemicarbazide, so that the expansion performance is remarkably improved (the combustion temperature in the test is 500 ℃), and other performances are also improved. In example 4, although the expansion performance is slightly better than that of example 5, the amount of the foaming agent is much higher than that of example 5, so the technical scheme of example 5 is inventive. From example 6, it can be seen that the effect of example 5 cannot be achieved by directly mixing the glass microspheres and the p-toluenesulfonyl semicarbazide, which indicates that the surface of the glass microspheres coated with the p-toluenesulfonyl semicarbazide in the invention is matched with each other to achieve a better foaming flame retardant effect. In example 7, too much coating of tosylsemicarbazide affects the spherical structure and adversely affects the blowing agent performance, indicating that the parameters need to be controlled within reasonable ranges.

Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. The foaming ceramic heat-insulation fireproof silicone sealant is characterized by comprising the following components in parts by weight: 100 parts of basic polymer, 2-25 parts of plasticizer, 20-100 parts of filler, 50-120 parts of flame retardant, 10-75 parts of glass powder, 0.5-15 parts of foaming agent, 0-5 parts of thixotropic agent, 3-20 parts of color paste, 3-15 parts of crosslinking agent, 0.2-5 parts of silane coupling agent and 0.015-0.3 part of catalyst; the base polymer comprises at least one of alpha, omega-dihydroxy polydimethylsiloxane and alkoxy-terminated polydimethylsiloxane.

2. The foamed ceramifying heat-insulating fireproof silicone sealant according to claim 1, wherein the plasticizer is at least one of polydimethylsiloxane, alkane mixture and polyethylene glycol.

3. The foamed ceramic heat-insulating fireproof silicone sealant as claimed in claim 1, wherein the filler is at least one of active nano calcium carbonate, light calcium carbonate, heavy calcium carbonate, diatomite, silica micropowder, kaolin, quartz powder, titanium dioxide and fumed silica.

4. The foamed ceramic heat-insulating fireproof silicone sealant as claimed in claim 1, wherein the flame retardant is at least one of modified hydrated metal oxide, metal boride, antimony trioxide, ammonium polyphosphate, melamine urea cyanate and calcium aluminate.

5. The foamed ceramic heat-insulating fireproof silicone sealant according to any one of claims 1 to 4, wherein the glass powder is at least one of aluminum oxide, silicon dioxide, boron trioxide, lithium oxide, sodium oxide, potassium oxide, barium oxide, calcium oxide, and magnesium oxide.

6. The intumescent ceramifying heat-insulating fire-retardant silicone sealant according to claim 1, wherein the foaming agent comprises at least one of p-toluenesulfonyl semicarbazide, 5-phenyltetrazole, azodicarbonic ammonium carbonate, glass microspheres, and diethyl azodicarboxylate.

7. The foamed ceramization heat-insulation fireproof silicone sealant according to claim 6, wherein the foaming agent is a p-toluenesulfonyl semicarbazide-coated glass microsphere, and the preparation method comprises the following steps:

1) drying the hollow glass microspheres, adding an aqueous solution of a coupling agent phenylaminomethyl triethoxysilane, stirring for 1-2h, and filtering to obtain coupling agent-coated hollow glass microspheres, wherein the mass of the coupling agent is 0.5-1% of that of the hollow glass microspheres;

2) adding dimethyl sulfoxide into p-toluenesulfonyl semicarbazide until the dimethyl sulfoxide is dissolved, adding the hollow glass microspheres coated with the coupling agent, wherein the mass ratio of the hollow glass microspheres coated with the coupling agent to the p-toluenesulfonyl semicarbazide is 1 (2-4), stirring for 1-2h, standing overnight, filtering, and drying at the temperature of 100 ℃ and 120 ℃ for 2-4h to obtain the glass microspheres coated with the p-toluenesulfonyl semicarbazide.

8. The foamed ceramization heat-insulating fireproof silicone sealant according to claim 1, wherein the thixotropic agent is at least one of polyamide wax and hydrogenated castor oil; the catalyst is at least one of isopropyl titanate, tetrabutyl titanate, di (ethyl acetoacetate) diisopropoxy titanate, di (acetylacetone) -1, 3-propylene dioxy titanium, dibutyltin dilaurate, dibutyltin diacetate, stannous octoate and chelated tin.

9. The foamed ceramifying heat-insulating fireproof silicone sealant according to claim 1 or 8, wherein the crosslinking agent is at least one of methyltrimethoxysilane, vinyltrimethoxysilane, methyltributanoxime silane, vinyltributoxime silane and phenyltributoxime silane; the silane coupling agent is at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane and glycidoxypropyltriethoxysilane.

10. The preparation method of the foamed ceramization heat-insulation fireproof silicone sealant as claimed in any one of claims 1 to 9, characterized by comprising the following steps:

A. putting a base polymer, a plasticizer, a filler, a flame retardant, glass powder, a foaming agent and a thixotropic agent into a kneader, controlling the oil temperature range at 110-;

B. and putting the base material, the color paste, the cross-linking agent, the silane coupling agent and the catalyst into a stirrer, controlling the vacuum degree to be 0.09-0.095MPa and the stirring frequency to be 80-120Hz, stirring for 0.5-1.5h, and removing the vacuum by nitrogen to prepare the foamed ceramic heat-insulating fireproof silicone sealant.

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